Resumen
The invention relates to a microporous crystalline, zeolitic material, which, in a calcinated and anhydrous state, has a chemical composition that is represented by formula: x (M1/>n<XO>2<): y YO>2<: z GeO>2<: (1-z) TO>2<, wherein x has a value lower than 0.2, y has a value lower than 0.1, z has a value lower than 1, the value of at least one amongst x, z e y being higher than zero; M is H+ or at least one +n charged inorganic cation; X is at least one chemical element with a +3 oxidation state, Y is at least one chemical element with a + oxidation state and T is at least one chemical element with a +4 oxidation state (Si, Ti, Sn, V), said material having a particular x ray diffraction pattern. The invention also relates to a method for preparing said material and to its utilization as catalyst in processes for the separation and transformation of organic compounds.
Reivindicaciones
1. A microporous crystalline material of a zeolite nature with a chemical composition in the calcinated and anhydrous state that can be represented by the empirical formula: x (M<1/n> XO<2> ) : y YO<2> : z GeO<2> : (1-z) TO<2> wherein x has a value below 0.2; y has a value below 0.1; z has a value below 1; being at least one of z, x and y above zero: M is H+ or, at least, an inorganic cation with +n charge; X is at least a chemical element in a +3 oxidation state; Y is one or various chemical elements in a + oxidation state; and T is at least a chemical element in a +4 oxidation state, where the material, in the as synthesised state, has an X-ray diffraction pattern with d(Å) interplanar spacing values and I/Io (%) relative intensities in agreement with 14.01 W 12.36 VS 9.15 W 4.94 M 3.92 VS 3.57 M 3.37 VS and where the calcinated and anhydrous material has an X-ray diffraction pattern with d(Å) interplanar spacing values and I/Io (%) relative intensities in agreement with: 14.11 VS 12.42 VS 9.13 M 4.96 W 3.91 M 3.59 W 3.38 M wherein W means weak, M medium and VS very strong. 2. A crystalline material according to claim 1, wherein T is Si; x has a value below 0.1, preferably below 0.02; y has a value below 0.05 and preferably below 0.02; and z has a value below 0.1. 3. A crystalline material according to claim 1, wherein T is Si; x has a value below 0.2, preferably below 0.1 and more preferably below 0.02; y is zero; z has a value below 0.1, preferably below 0.1. 4. A crystalline material according to claim 1, wherein T is Si; y has a value below 0.1, preferably below 0.05 and more preferably below 0.02; z has a value below 1, preferably below 0.1. 5. A microporous crystalline material according to claim 1, wherein M is H, T is Si, y is zero; x has a value below 0.2, preferably below 0.1 and more preferably below 0.02, and z has a value below 1 and preferably below 0.1. 6. A microporous crystalline material according to claim 1, wherein T is Si, x and y are zero, z has a value below 1 and preferably below 0.1. 7. A microporous crystalline material according to claim 1, wherein z and y are zero, and wherein T is selected from Si, Ti, Sn, V and combinations thereof. 8. A microporous crystalline material according to any of claims 1, 2 and 4, wherein Y is selected from Ti, Sn, V and combinations thereof. 9. A microporous crystalline material according to any of claims 1, 2, 3 and 7, wherein X is selected from Al, Ga, B, Cr and combinations thereof. 10. A method for synthesising the microporous crystalline material in accordance with one of claims 1-9, in which one reaction mixture which contains a SiO<2> source, optionally a GeO<2> source, optionally a source of at least one other tetravalent Y element, preferably Ti, V or Sn. optionally a source of at least one other trivalent X element, preferably Al, Ga, Fe or Cr, an organic 1, 3,3,-tri-methyltricycle-6-azonium-[3.2.1.4<6,6> ] dodecane cation, and water is subjected to heating at a temperature of between 80 and 200ºC, preferably between 130 and 200ºC, until crystallisation has been achieved, in which the reaction mixture has a composition, in terms of molar ratios, within the following ranges ROH / SiO<2> = 0.01 - 1.0, preferably 0.1 - 1.0. M<1/n> OH / SiO<2> = 0-1.0, preferably 0-0.2. X<2> O<3> / SiO<2> = 0-0.1, preferably 0-0.05 and more preferably 0-0.01. YO<2> / SiO<2> = 0-0.1, preferably 0-0.05 and more preferably 0-0.02. GeO<2> / (SiO<2> + GeO<2> ) less than 1, preferably less than 0.1. H<2> O / SiO<2> = 0-100, preferably 1-50, more preferably 1-15. wherein M is H+ and at least one inorganic cation with +n charge; X is at least one trivalent element, preferably Al, B, Ga, Fe; Y is at least one tetravalent element, preferably Ti, Sn, V; and R is the organic cation, preferably 1,3,3,-tri-methyltricycle-6-azonium-[3.2.1.4<6,6> ] dodecane. 11. A method according to claim 10, in which the 1,3,3,-tri-methyltricycle-6-azonium-[3.2.1.4<6,6> ] dodecane organic cation is added in the form of hydroxide or in the form of a mixture of hydroxide and another salt, preferably a halide. 12. A method according to claim 10, wherein a quantity of the crystalline material is added to the reaction mixture as a crystallisation promoter, said quantity being in the range of 0.01 to 15% by weight with respect to the total silica added, preferably 0.05 to 5%. 13. A method according to claim 12, in which the crystallisation promoter is a microporous crystalline material as defined in any one of claims 1 to 9. 14. A method for use of a microporous crystalline material defined in any one of claims 1 to 9, as a catalyst in a process selected among cracking, hydro-cracking, soft hydro-cracking of hydrocarbons and/or functionalised hydrocarbons, hydro-isomerisation of olefins, alkylation of olefins with iso-paraffins, alkylation of aromatics with olefins or alcohols, and alkylation of benzene with propylene. 15. A method for use of a microporous crystalline material defined in any one of claims 1 to 9, as an oxidant in a selective oxidation process of organic compounds using H<2> O<2> , organic peroxides or hydroperoxides as oxidants. 16. A method for use of a microporous crystalline material, defined in any one of claims 1, 2, and 4, in which Y is partially Sn, as a catalyst in a process of the Baeyer-Villiger type. 17. A method for use of a crystalline material, defined in any one of claims 1-9, as a catalyst in an oxidation process of the Meerwein-Pondorf-Verley type. 18. A method for use of a microporous crystalline material defined in any one of claims 1, 2, and 4, in which Y is partially Ti, as a catalyst in a process selected from among processes from the epoxidation of olefins, oxidation of alkanes, oxidation of alcohols and oxidation of thioethers to sulphoxides and sulphones using organic or inorganic hydroperoxide, as oxidating agents.
